JPH10101673A - Production of metallophthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a metallophthalocyanine compound by a urea method in one step from reaction to purification capable of contracting the process, lowering a processing cost and simply removing a solvent without toxicity in the solvent, by using polyethylene glycol dialkylether as a reaction solvent. SOLUTION: This metallophthalocyanine compound is obtained by heating a phthalic acid derivative such as phthalic acid anhydride or imide phthalate, urea and a metal chloride such as copper(I) chloride, cobalt chloride (hexahydrate) or nickel chloride in the presence of a condensation catalyst such as ammonium molybdate and using polyethylene glycol dialkyl ether, preferably polyglyme as a reaction solvent, in capable of removing the solvent from a reaction product with a simple process such as filtration and washing without requiring a process subjecting the solvent to reduced pressure distillation after finishing the reaction, without problems such as adhering of the reaction product onto the device wall or impossibility of stirring, at a high purity and high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a metal phthalocyanine compound, and more particularly to a simple method for producing a high-purity metal phthalocyanine compound.

[0002]

2. Description of the Related Art Metal phthalocyanine compounds have a clear hue from blue to green, a large coloring power, excellent fastness and durability, and are widely used in the fields of paints, plastic coloring, printing inks and the like. ing. In recent years, optical recording materials, photoconductive materials, and functional materials such as catalysts have been actively studied and used.

[0003] Metal phthalocyanine is generally produced by a urea method (Wyler method, phthalic anhydride liquid phase method), a phthalonitrile method or the like. The phthalonitrile method is a method using phthalonitriles as a raw material, and has the advantages that the reaction time is relatively short and the yield is good. But,
Phthalonitriles used as raw materials are expensive and the production cost is high. In addition, phthalonitriles have been pointed out to be toxic, and their handling requires care in terms of safety and health.

On the other hand, the urea method, particularly the phthalic anhydride liquid phase method, is a method in which phthalic acids, urea, a metalating agent and a catalyst are heated in a solvent. Since these raw materials are inexpensive and have low toxicity, the urea method is low-cost and safe. However, since a hydrophobic organic solvent such as nitrobenzene or trichlorobenzene is usually used as the solvent, it is necessary to separate and recover the solvent from the reaction mixture after the reaction is completed.

When distilling off the solvent from the reaction mixture, a high temperature is maintained under reduced pressure so as not to bump the reaction mixture. This operation is very complicated and takes a long time especially when the reaction is performed on a large scale. Therefore, the urea method has a drawback that the production process is complicated particularly in mass production. Also, hydrophobic organic solvents are usually harmful to the human body and the environment,
Difficult to handle.

Since the phthalic anhydride solid phase method does not use an organic solvent as a reaction solvent, there is no complication due to separation and recovery of the organic solvent. However, this method is not suitable for mass production due to low yield.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to eliminate the necessity of distilling a solvent from a reaction mixture after completion of a reaction.
It is an object of the present invention to provide a high-yield, low-cost, safe and simple method for producing a metal phthalocyanine compound.

[0008]

That is, the present invention relates to a method for producing a phthalocyanine compound by a urea method,
An object of the present invention is to provide a method for producing a metal phthalocyanine compound, characterized by using polyethylene glycol dialkyl ether as a reaction solvent, thereby achieving the above object.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Urea method (phthalic anhydride liquid phase method)
Is generally a method for producing a metal phthalocyanine compound by heating a phthalic acid derivative such as phthalic anhydride and phthalimide, urea and a metal chloride in an inert organic solvent in the presence of a condensation catalyst. is there. This method is well known and is described, for example, in "Dyes and Chemicals", Vol.
No. 0, pages 213 to 215, 1978,-Recent phthalocyanine pigment production technology [I]-and the like.

Examples of the phthalic acid derivative used as a raw material include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 4-sulfophthalic acid, alkyl-substituted phthalic acid, alkoxy-substituted phthalic acid, and 4-nitrophthalic acid. Acid imide, 4-chloro-5-nitrophthalimide, ammonium salt of phthalic acid, metal phthalate (Na, K),
Examples include phthalic esters, phthalamides, phthalyl halides, phthalimides, orthocyanobenzoic acid, and orthocyanobenzoates.

Examples of metal chlorides include copper (I) chloride, cobalt chloride (hexahydrate), and iron chloride (II, II).
I), nickel chloride, aluminum chloride and the like. Polyvalent metal sulfate (eg, copper sulfate, aluminum sulfate, chromium sulfate), nitrate (eg, copper (II) nitrate), polyvalent metal phosphate, or polyvalent metal borate instead of metal chloride Etc. may be used.

Examples of the condensation catalyst include ammonium molybdate, molybdate, sodium molybdate, silicomolybdate, phosphomolybdate, molybdenum oxide, ammonium phosphomolybdate, phosphotungstomolybdate, and molybdenum carbonyl. In particular, ammonium molybdate is common and preferred.

As the inert organic solvent, polyethylene glycol dialkyl ether is used. The polyethylene glycol dialkyl ether refers to a compound represented by the following formula (1).

R ¹ O (CH ₂ CH ₂ O) _n R ² (1)

In the formula, R ¹ and R ² independently represent a group having 1 carbon atom
To 8, preferably an alkyl group having 1 to 4 carbon atoms, and n
Is 2 or more, preferably 2 to 10, more preferably 3 to
Indicates an integer of 5.

As specific examples, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), polyethylene glycol dimethyl ether (a mixture of polyglymes having n of 2 or 3 or more), diethylene glycol diethyl ether , Triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like. These can be used alone or in combination.

In formula (1), polyethylene glycol dimethyl ether in which R ¹ and R ² are both methyl groups (generally called polyglyme) is preferred. Particularly preferred are polyglymes having a boiling point of 180 ° C. or higher, such as triglyme and tetraglyme.

Polyglyme has excellent miscibility with phthalic acid derivatives and products, is inert to the above-mentioned reaction components such as phthalocyanine derivatives, is water-miscible,
Not toxic. As a result, by using polyglyme as the inert organic solvent, the reaction proceeds in a fine state without forming a reactant, that is, a uniform slurry reaction is possible, and high temperature (about 180 to about 200 ° C.) , And can be removed with water, and handling is safe.

In the method for producing a metal phthalocyanine of the present invention, the above-mentioned reaction components are subjected to a condensation reaction by heating in an inert organic solvent. The amount of each reaction component used is 3 moles or more of urea, preferably 3 to 1 mole per mole of the phthalic acid derivative.
6 mol, 0.1 to 5% mol of condensation catalyst, preferably 0.1 to 5 mol
1% mol, 1/4 mol or more of metal chloride, preferably 1 /
It is 4 to 1/2 mol. The amount of the inert organic solvent to be used is not particularly limited. In the case of polyglyme, the amount is 2 times or more, preferably 4 to 6 times the weight of the phthalic acid derivative.

The condensation reaction is carried out at 180 to 200 ° C. for 2 to 10
Do time. A preferred embodiment is 2-30 at about 130-160 ° C.
The reaction is carried out for 4 hours, more preferably for 4 hours or more at 180 to 200 ° C, preferably for 4 to 10 hours.

After the completion of the condensation reaction, the reaction mixture is allowed to cool to about 100 ° C., and hot water (about 80 ° C.) is added to the reaction mixture.
Stir for 3 hours. Thereafter, the reaction mixture is subjected to hot filtration and hot water washing several times to remove an inert organic solvent and inorganic impurities by-produced. Since the organic solvent used in the method of the present invention is water-soluble, it can be easily separated from the reaction product by washing with water. If necessary, it is further washed with acetone or DMF and dried to obtain a metal phthalocyanine.

The metal phthalocyanine obtained here is generally insoluble in water. However, metal phthalocyanine carboxylic acid amides and the like can be made water-soluble by hydrolysis. The hydrolysis is an operation for converting the produced water-insoluble metal phthalocyanine into a water-soluble metal phthalocyanine having a carboxyl group in particular (eg, metal phthalocyanine tetracarboxylate).

Methods for hydrolyzing metal phthalocyanine carboxamides are well known to those skilled in the art. For example, after removing the organic solvent in the above-described method, the obtained water-insoluble metal phthalocyanine wet cake is dispersed in a 5 to 30% aqueous solution of an alkali (eg, sodium hydroxide and potassium hydroxide), Stirring is added under reflux for hours. Upon cooling, a mineral acid (eg, concentrated hydrochloric acid, sulfuric acid) is added to obtain a slurry. The slurry is filtered and washed with hot water or redispersed in water to remove salts, inorganic and organic impurities,
If necessary, washing with acetone or DMF and drying are performed to obtain a water-soluble metal phthalocyanine.

[0024]

Since phthalic acid derivatives hardly condense in a hydrophilic organic solvent and hardly form (copper) phthalocyanine, they are a raw material for directly synthesizing finer phthalocyanine pigments than phthalonitrile and iminoisoindolenin. Reported as inappropriate ("Dyes and chemicals,"
Vol. 3, No. 11, pp. 225-227, 1978,-
Recent phthalocyanine pigment production technology [II]-). Therefore, hydrophilic organic solvents have heretofore been considered unsuitable as organic solvents used in the urea method.

For example, as shown in Comparative Examples 3 and 4 below, when an alcoholic water-soluble solvent such as polyethylene glycol or ethylene glycol monoethyl ether (ethyl cellosolve) is used as the solvent, the desired metal phthalocyanine Was hardly obtained.

However, the present inventors have found that metal phthalocyanine can be synthesized in high yield by the urea method when a specific hydrophilic organic solvent such as high-boiling polyethylene glycol dialkyl ether (for example, polyglyme) is used.

According to the method of the present invention, generally, a metal phthalocyanine represented by the following formula (2) can be preferably produced.

[0028]

Embedded image

In the formula, R represents a nitro group, a halogen atom, an alkyl group, an alkoxy group, an amino group, a carboxyl group, an alkali metal salt of a carboxyl group, etc., and Met represents Cu,
Shows multivalent metals such as Co, Fe, Ni, Al, and Cr.

The thus obtained metal phthalocyanine of the present invention is useful as a deodorant, an optical recording material, a photoconductive material, a coloring dye and pigment, or a functional dye.

For example, water-insoluble tetranitro copper phthalocyanine is useful as a precursor of functional phthalocyanine for various uses. The nitro compound can be reduced to obtain tetraamino copper phthalocyanine. Furthermore, various diazo copper phthalocyanine derivatives can be obtained by diazotizing the amino compound.

[0032] Water-soluble cobalt phthalocyanine tetracarboxylate, iron (III) octacarboxylate phthalocyanine having a carboxyl group in the phthalocyanine nucleus are useful as deodorants.

The water-soluble phthalocyanine having a carboxyl group or a sulfonic group in the phthalocyanine nucleus is also useful as a coloring agent for aqueous inks and color filters.

In addition, for example, tetraisopropoxy metal phthalocyanine and tetrabutyl metal phthalocyanine having an alkoxy group or an alkyl group in the phthalocyanine nucleus are
Used in optical recording materials as near infrared absorbing dyes.

[0035]

The method of the present invention has the following advantages as compared with the conventional urea method, is capable of shortening the process and reducing the production cost, and is suitable for industrial mass production of metal phthalocyanine compounds. Is extremely advantageous. i) The solvent can be removed from the reaction product by simple steps of filtration and washing with water, and a step of distilling the solvent under reduced pressure after completion of the reaction is unnecessary. ii) As a result, it is possible to carry out from the reaction to the purification in a one-step continuous process. iii) Problems such as adhesion of reaction products to the vessel wall and inability to stir do not occur. iv) The solvent has no toxicity and is safe in handling. v) Therefore, a metal phthalocyanine having high purity and stable quality can be obtained by a high yield, simple and safe operation.

[0036]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Synthesis of tetranitrocopper phthalocyanine A 4-ml nitrophthalimide was placed in a 5000 ml glass four-necked flask equipped with necessary equipment such as a stirrer and a reflux tube.
0 g, urea 660 g, ammonium molybdate 20
g, 70 g of copper (I) chloride and 2500 g of triglyme, and the mixture was stirred at 130 ° C. for 1 to 2 hours, then at 160 ° C. for 2 hours, and then at 180 ° C. for 4 hours.
Stirred for hours.

After cooling to about 100 ° C., 2500 g of hot water at about 80 ° C. was gradually added to the reaction mixture, and the mixture was further stirred under reflux for 2 to 3 hours. After filtration while hot, washing was performed by sprinkling with 10 L (liter) of hot water. After drying, the desired compound 4
60 g were obtained with a yield of 93.6%. Table 1 shows the results of elemental analysis and the yield of this compound.

Example 2 Synthesis of Cobalt Phthalocyanine Tetracarboxylate In a 10000 ml glass four-necked flask equipped with necessary equipment such as a stirrer and a reflux tube, trimellitic anhydride 115 was added.
2 g, urea 1800 g, ammonium molybdate 10
g, cobalt chloride hexahydrate 360 g and triglyme 3
000 g were charged and the mixture was stirred at 130 ° C. for 1 hour and subsequently at 200 ° C. for 4 hours.

After cooling to about 100 ° C., 5000 g of hot water at about 80 ° C. was gradually added to the reaction mixture, and the mixture was further stirred under reflux for 2 to 3 hours. After filtration while hot, the product was sprinkled and washed with 30 L of hot water. Next, the obtained wet cake was poured into 6000 parts of a 20 to 30% aqueous potassium hydroxide solution, and stirred under reflux for 12 hours. The reaction mixture was cooled using a water / ice bath, 4130 g of concentrated hydrochloric acid was added dropwise so as not to exceed 30 ° C., and the mixture was further stirred for 1 hour. The obtained slurry was collected by filtration, sprinkled and washed with 80 to 100 L of water to remove salts, and then dried to obtain the desired compound 69.
3.4 g were obtained with a yield of 61.9%. Table 2 shows the results of elemental analysis, the yield, and the molecular absorption coefficient ε of this compound.

Example 3 Synthesis of Iron (III) Tetracarboxylate Phthalocyanine In a 5000 ml glass four-necked flask equipped with necessary equipment such as a stirrer and a reflux tube, trimellitic anhydride 384 was added.
g, urea 600 g, ammonium molybdate 2 g, iron (III) chloride 81 g and tetraglyme 1500 g, and the mixture was stirred at 130 ° C. for 1 hour.
Stirred at 80 ° C. for 6 hours.

After cooling to about 100 ° C., 2500 g of hot water at about 80 ° C. was gradually added to the reaction mixture, and the mixture was further stirred under reflux for 2 to 3 hours. After filtration while hot, washing was performed by sprinkling with 15 L of hot water. Next, the obtained wet cake was put into 3000 parts of a 20 to 30% aqueous potassium hydroxide solution, and stirred under reflux for 12 hours.

The reaction mixture was cooled using a water / ice bath, 2065 g of concentrated hydrochloric acid was added dropwise so as not to exceed 30 ° C., and the mixture was further stirred for 1 hour. The obtained slurry was collected by filtration, and water 20
The salt was removed by sprinkling and washing with ５０50 L, followed by drying to obtain 265 g of the desired compound in a yield of 71.2%.
I got it. Table 1 shows the results of elemental analysis and the yield of this compound.

Example 4 Synthesis of iron (III) phthalocyanine octacarboxylate In a 5000 ml glass four-necked flask equipped with necessary equipment such as a stirrer and a reflux tube, 300 g of trimellitic anhydride dianhydride, 600 g of urea, and molybdenum Ammonium acid 1
0 g, iron chloride (III) 100 g and tetraglyme 15
Then, the mixture was stirred at 130 ° C. for 1 hour, followed by stirring at 200 ° C. for 8 hours.

After cooling to about 100 ° C., 2500 g of hot water at about 80 ° C. was gradually added to the reaction mixture, and the mixture was further stirred under reflux for 2 to 3 hours. After filtration while hot, washing was performed by sprinkling with 15 L of hot water. Next, the obtained wet cake was put into 3000 parts of a 5 to 10% aqueous potassium hydroxide solution, and stirred under reflux for 2 hours.

The reaction mixture was cooled using a water / ice bath, 520 g of concentrated hydrochloric acid was added dropwise so as not to exceed 30 ° C., and the mixture was further stirred for 1 hour. The obtained slurry was collected by filtration, and water 20 ~
The salt was removed by sprinkling and washing with 50 L, followed by drying to give 160 g of the desired compound in a yield of 51.0%.
I got it. Table 1 shows the results of elemental analysis and the yield of this compound.

Example 5 Synthesis of cobalt phthalocyanine In a 10-L glass four-necked flask equipped with necessary equipment such as a stirrer and a reflux tube, 741 g of phthalic anhydride and 150 g of urea were placed.
0 g, 10 g of ammonium molybdate, 328 g of cobalt chloride hexahydrate and 3500 g of triglyme, and the mixture was stirred at 130 ° C. for 1 hour.
Stirred at 0 ° C. for 6 hours.

After cooling to about 100 ° C., 4000 g of hot water at about 80 ° C. was gradually added to the reaction mixture, and the mixture was further stirred under reflux for 2 to 3 hours. After filtration while hot, the product was sprinkled and washed with 30 L of hot water. After drying, 636 g of the desired compound was obtained in a yield of 89.1%. Table 1 shows the results of elemental analysis and the yield of this compound.

Various metal phthalocyanines were synthesized by replacing the phthalocyanine-forming material, the metallizing agent and the reaction solvent used in the above Examples with the above-mentioned phthalic acids or their functional derivatives and metal agents, respectively. The results were all good, and a high-purity metal phthalocyanine that did not require a pigmentation treatment could be directly synthesized (one pot).

Comparative Example 1 Synthesis of Cobalt Phthalocyanine Tetracarboxylate 3.84 of trimellitic anhydride was placed in a 100 ml glass four-necked flask equipped with necessary equipment such as a stirrer and a reflux tube.
g, urea 12.0 g, ammonium molybdate 0.5
g, 1.30 g of cobalt chloride hexahydrate and 60 g of nitrobenzene, and a condensation reaction was carried out according to a conventionally known Weyler method.

After the nitrobenzene solvent was removed from the reaction mixture under reduced pressure, 100 ml of hot water was added to the system, and the mixture was further stirred while heating. After filtration, 60 m in the same manner as in Example 2.
l of 20-30% aqueous potassium hydroxide solution,
The desired compound 3.6 was obtained by filtration, washing with water and drying.
5 g were obtained with a yield of 97.7%. Table 2 shows the results of elemental analysis, the yield, and the molecular absorption coefficient ε of this compound.

Comparative Example 2 Synthesis of Cobalt Phthalocyanine Tetracarboxylate Except that the reaction solvent nitrobenzene used in Comparative Example 1 was replaced with trichlorobenzene,
3.90 g of the desired compound was obtained in a yield of 104.4%. Table 2 shows the results of elemental analysis, the yield and the molecular absorption coefficient ε of this compound.
Shown in

Comparative Example 3 Synthesis of cobalt phthalocyanine tetracarboxylate The reaction was carried out in exactly the same manner as in Example 2 except that the reaction solvent (triglyme) used in Example 2 was changed to diethylene glycol. Could not be obtained.

Comparative Example 4 Synthesis of iron (III) phthalocyanine tetracarboxylate The reaction solvent (tetraglyme) used in Example 3 was ethylene glycol monoethyl ether (ethyl cellosolve).
The reaction was carried out in exactly the same manner as in Example 3 except that the phthalocyanine was replaced with, but the desired phthalocyanine was not obtained.

[0055]

Table 1 Example 1 Example 3 Example 4 Example 5 Yield (%) 93.6 71.2 51.0 89.1 Elemental analysis Theoretical measured value Theoretical measured value Theoretical measured value Theoretical measured Value C 50.56 50.33 58.06 56.37 52.17 47.18 67.25 68.36 H 2.11 2.08 2.15 2.29 1.74 2.27 2.80 2.31 N 22.12 23.50 15.05 16.18 12.17 14.85 19.61 20.71 Metal 8.36 8.42 7.53 4.67 6.09 4.47 10.3 7.90 (Cu) (Fe) (Fe) (Co)

[0056]

Table 2 Example 2 Comparative Example 1 Comparative Example 2 Yield (%) 61.9 97.9 104.4 ε (λ1) 37500 27500 42500 ε (λ2) 47000 37000 33800 Elemental analysis Theoretical value Measured value Theoretical value Measured Value Theoretical value Measured value C 57.83 57.40 57.83 53.23 57.83 53.03 H 2.14 2.08 2.14 1.31 2.14 0.81 N 14.99 14.36 14.99 15.36 14.99 15.13 Metal 7.90 7.82 7.90 7.69 7.90 7.08 (Co) (Co) (Co)

In Examples 1 to 5, the reaction product from which the solvent was removed after the condensation reaction was a uniform slurry. On the other hand, in Comparative Examples 1 and 2, the phenomenon of adhesion and solidification of the reaction product on the vessel wall occurred, and some stirring was impossible. A high yield is obtained in the comparative example, which is due to the large amount of impurities produced as a by-product of this reaction. This means that Example 2 and Comparative Examples 1 and 2 shown in Table 2 were used.
It is clear from the molecular extinction coefficient and the result of elemental analysis for

Further, in order to examine the purity of the product,
The infrared absorption spectra of cobalt phthalocyanine tetracarboxylate of Example 2 and Comparative Example 1 are shown in FIG. 1 and FIG. Both have absorptions of each characteristic derived from cobalt phthalocyanine tetracarboxylate, and it is apparent from the spectrum that the carbonyl absorption (v _{C = O} ) in Example 2 is about 1
At 700 cm ^-1 , the intensity is as strong as the absorption derived from the phthalocyanine skeleton, but in Comparative Example 1, the carbonyl absorption (ν
It can be seen that the relative intensity of _{C = O} ) is weak and the purity is low. Similar results were obtained for Comparative Example 2.

[Brief description of the drawings]

1 shows an IR spectrum of cobalt phthalocyanine tetracarboxylate obtained in Example 2. FIG.

FIG. 2 shows an IR spectrum of cobalt phthalocyanine tetracarboxylate obtained in Comparative Example 1.

Claims (2)

[Claims] 1. A method for producing a metal phthalocyanine compound by a urea method, wherein a polyethylene glycol dialkyl ether is used as a reaction solvent. 2. The method according to claim 1, wherein said polyethylene glycol dialkyl ether is polyglyme.